Production of c-alkyl and c-aralkyl derivatives of aromatic compounds



Patented Feb. 14, 1933 UNITED STATES PATENT OFFICE ZOL'IAN FOLDI, OF BUDAPEST, HUNGARY, ASSIGNOR TO I. G. IARBENINDUSTRIE .AKTIEN'GESELLSOHAIT, OF FRANKFORT-ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY PRODUCTION OF C-ALKYL AND C-ARALKYL DERIVATIVES OF AROMATIC COMPOUNDS No Drawing. Application fil eii September 12, 1929, Serial No. 392,251, and in Hungary September 19, 1928.

' sulphonic esters of the lower aliphatic alcohols only exert C-alkylating action at high temperatures, between 200 and 300 centigrade, at which temperatures, however, a

g complicated reaction takes place. Not only m0no-, but also poly-alkyl derivatives are formed andia part of the material is resinified. The sulphonic acid esters of unsaturated aliphatic alcohols, as for example benzene sulphonic allyl ester, on the contrary react with aromatic compounds at much lower temperatures, between 100 and 150 centigrade. Moreover under'still more favourable conditions the sulphonic esters of substituted aliphatic alcohols, as for example benzyl alcohol or phenyl ethyl carbinol, exert'a C- alkylating action. The sulphonic esters of the latter alcohols are particularly suitable for the introduction of aralkyl groups into i the benzene nucleus or into any other aromatic nucleus.

By the process according to the present invention important intermediate products useful for organic chemical manufacture on a large scale, and also excellent'wetting agents by subsequent sulphonation' of the products, may be prepared.

The following examples will further illustrate how the said invention may be carried out in practice, but the invention is not restricted to these examples. The parts are by weight.

Example 1 100 parts of toluene sulphonic ethyl ester and 200 parts of benzene are heated in a tube for several hours at 300 centigrade. After ing to the equation:

drocarbons.

cooling the toluene sulphonic acid is washed out with water and the benzene layer is fractionated. After. the removal of the unchanged benzene, ethyl benzene, then diethyl benzene and finally a little triethyl benzene distil over. The reaction proceeds accordon, v can,

I Oz-O-OQHr i Q OH and homologues.

' Example 2 100 parts of benzene sulphonic allyl ester and 350 parts of xylene are boiled under a reflux condenser. After boiling for a short period of time benzene sulphonic acid separates out and this is dissolved out with water. The excess of xylene is removed by fractional distillation. parts of an oil remain behind which by fractional distillation in a high vacuum may be separated into unsaturated hydrocarbons and a resin formed by the polymerization of the unsaturated hy- The reaction proceeds according to the equation:

and homologues.

Elwample 3 The reaction proceeds according to the equat1on:

Earample 4 Dinitrobenzene is heated with half its weight of toluene sulphonic benzyl ester to 150 centigrade. he sulphonic acid formed is washed out and the unchanged dinitrobenzene is separated from benzyl-dinitrobenzene by distillation in a high vacuum. The

' latter compound melts at from 183 to 185 centigrade. The reaction to the equation:

proceeds according Example 5 50 parts of benzen sulphonic benzyl ester and 150 parts of phenol are heated to 150 centigrade. The sulphonic acid formed and the remainders of phenol are removed in the usual manner. From the remaining mixture of benzylphenols the ortho and para derivatives are separated by the usual methods for example by crystallization or on the basis of their different acidity. The yields are: paraof the theoretical yield. The reaction proceeds according to the equation:

7 Ewample 6 25 parts of benzene sulphonic benzyl ester and 100 parts of anisol are boiled for a short time. The further working up is carried out in the manner described in the foregoing examples. The yield of benzyl anicol amounts to 80 per cent of the theoretical amount. The reaction proceeds according to the equation:

Example 7 I 25 parts of benzene sulphonic benzyl ester COOOH: l I

SOzOH Example 8 COOCH;

benzylphenol from 2 1 30 P Cent and 25 parts of benzene sulphonic benzyl ester 65 ortho-benzylphenol from 30 to -10 per cent and 50 parts of ethyl cinnamate are heated to 130 centigrade. After removing the sulphonic acid formed, the remainder is fraca sulphonating agent. The reactionproceeds according to the equation:

OaOH H:

What I claim is A 1. The process for producing C-alkyl derivatives of aromatic compounds which comprises reacting from neutral to acid aromatic compounds while heating with an alkyl ester of an aromatic sulphonic acid.

52.- The process for producing C-alkyl derivatives of aromatic compounds which comprises reacting from neutral to acid aromatic compounds while heating with an alkyl ester ofanaromatic monocyclic sulphonic acid." 3. The process for producing C-alkyl de- CH=GH OOOC:H; oH=o-oooo=m i r H2 ---o m-o-om-G Ewample rivatives of aromatic compounds which com- Naphthalene sulphonic butyl ester is heat- M ed for about several hours to from about 0 200 to 250 C. The product obtained is soluble in water and possesses, as free acid as well as in the form of alkali metal salts thereof, a very good wetting, cleansing and dispersing power. In this case one part of the sulphonic ester reacts with the other part thereof. The reaction proceeds according to the equation:

100 parts of naphthalene sulphonic acid are heated for some time with 50 parts of benzene sulphonic benzyl ester to about 150 C. When a little water has been added heating to about 80 C. is sufficient. The product obtained is soluble in .water and constitutes a highly eiiicient wetting, cleansing and disperslng agent. A similar product is obtained when naphthalene is treated with the said benzene sulphonic ester in the aforedescribed 5 manner and the product is then treated with prises reacting from neutral to acid aromatic compounds while heating with an ester of benzene sulphonic acid with an aliphatic alcohol. 4. The process for producing C-alkyl derivatives of aromatic compounds which comprises reacting from neutral to acid aromatic compounds while heating with an ester of benzene sulphonic acid with an aliphatic alcohol substituted by an aromatic. radicle.

5. The process for producing 'C-alkyl derivatives of aromatic compounds'which comprises reacting from neutral to acid aromatic compounds while heating with benzene sulphonic benzyl ester.

6. The process for producing C-alkyl derivatives of aromatic compounds which comprises heating a from neutral to acid naphthalene compound with an alkyl ester of an aromatic sulphonic acid.

7. The process for producing C-alkyl derivatives of aromatic compounds which comprises heating a naphthalene sulphonic ester Wltl an alkyl esterv of an aromatic sulphonic aci 8. The process for producing C-alkyl derivatives of aromatic compounds which comprises heating a from neutral to acid naphthalene compound with a naphthalene sulphonic alkyl ester.

9. The process for producing G-alkyl derivatives of aromatic compounds which comprises heating a polynuclear, from neutral to acid aromatic compound with an alkyl ester of an aromatic sulphonic acid. a

10. The process for producing C-alkyl de- 5 rivatives of aromatic compounds which comprises heating a sulphonic acid of a polynuclear, from neutral to acid aromatic compound with an ester of an aromatic sulphonic acid with an aliphatic alcohol containing more than two carbon atoms.

11. The rocess for producing C-alkyl derivatives 0% aromatic compounds which comprises heating naphthalene sulphonic butyl ester to from about 200 to about 250 C.

In testimony whereof I have hereunto set my hand.

ZOLTAN FGLDI. 

